CN100494493C - Phosphorization liquid for forming amorphous film coating on iron and zinc surface - Google Patents
Phosphorization liquid for forming amorphous film coating on iron and zinc surface Download PDFInfo
- Publication number
- CN100494493C CN100494493C CNB2005101152661A CN200510115266A CN100494493C CN 100494493 C CN100494493 C CN 100494493C CN B2005101152661 A CNB2005101152661 A CN B2005101152661A CN 200510115266 A CN200510115266 A CN 200510115266A CN 100494493 C CN100494493 C CN 100494493C
- Authority
- CN
- China
- Prior art keywords
- crystalline state
- concentration
- zinc surface
- acid
- phosphatization liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Chemical Treatment Of Metals (AREA)
Abstract
Phosphorization solution for coating amorphous film on the surface of Fe and Zn comprises: first generation phosphate 0.002-0.1mol/L containing one or more of Zn2+, Fe2+, Ca2+, Al2+, amorphous phosphorization catalyst 0.001-0.05mol/L containing one or more of ethanedioic acid, citric acid, tartaric acid, cyclohexanhexol hexa-phosphonic acid, hydroxyethyl di-phosphonic acid and EDTA or the derivants, oxidizing agent 0.001- 0.05mol/L containing one or more of chlorate, nitrate, superoxide, neutralizer containing one or more of sodium hydrate, sodium carbonate and ammonia water for adjusting the free acidity of the solution to 0.0+-1.5. The organic acid or derivants has complexation or chelate ability with metal ions. The film has the advantages of low porosity, good adhesive power with steel and zinc material, and low cost.
Description
Technical field: the present invention relates to a kind of phosphatization liquid, particularly a kind of phosphatization liquid that can obtain the non-crystalline state rete at iron and steel, zinc and zinc base alloy (comprising zinc coating) product surface.
Background technology: in background technology, divide, can be divided into crystalline state and non-crystalline state by the structure of phosphatize phosphate coat.Can better suppress underfilm corrosion, sticking power characteristics preferably though the crystalline state phosphatize phosphate coat has, have that phosphatization intergranule hole is more, must show to mediate before the phosphatization and generally need carry out the passivation sealing of hole after reason and the phosphatization and handle and make production more numerous and diverse and defectives such as the sticking power between the pot galvanize product surface coating are unreliable; And the non-crystalline state phosphatize phosphate coat, though have that porosity is lower, needn't show to mediate before the phosphatization and need not carry out sealing treatment after reason and the phosphatization and make the easy characteristics of producing, and normally adopt to add molybdate or tungstate film forming, exist on the steel product phosphatize phosphate coat ADHESION OF PAINTS power is lower than the crystalline state phosphatize phosphate coat, ADHESION OF PAINTS power is subjected to a certain degree limiting and because the cost defective such as rise significantly along with the rising significantly of molybdenum, tungsten compound price in recent years on the pot galvanize goods.For overcoming these defectives, the phosphatization liquid of iron and zinc surface acquisition non-crystalline state rete is developed.
Summary of the invention: technical problem to be solved by this invention is to provide a kind of iron and zinc surface to obtain the phosphatization liquid of non-crystalline state rete, it can obtain the lower phosphatize phosphate coat of porosity (being lower than crystalline state phosphatize phosphate coat and the common non-crystalline state phosphatize phosphate coat that contains molybdenum, tungsten compound) effectively, to steel and zinc (comprising pot galvanize) goods ADHESION OF PAINTS power better (being better than the common non-crystalline state phosphatize phosphate coat that contains molybdenum, tungsten compound), cost lower (be about crystalline state phosphatize phosphate coat cost 55%, the common non-crystalline state phosphatize phosphate coat cost that contains molybdenum, tungsten compound 42%), produce easy.
The technical scheme that the present invention solves its technical problem employing is that it comprises following component:
By more than one Zn
2+, Fe
2+, Mn
2+, Ca
2+, Mg
2+, Ni
2+, Al
2+The concentration that metal ion constitutes is the primary phosphate of 0.002～0.1mol/L,
The concentration that is made of hydroxyethyl di 2 ethylhexyl phosphonic acid, ethylenediamine tetraacetic phosphonic acids, the organic acid or derivatives thereof of EDTA in more than one the oxalic acid, propanedioic acid, maleic acid, citric acid, tartrate, bios six phosphoric acid, phosphonate derivative is the non-crystalline state phosphorization filming catalyzer of 0.001～0.05mol/L, this organic acid or derivatives thereof and above-mentioned metal ion have complexing or sequestering power
The concentration that is made of more than one oxymuriate, nitrate, nitrite, superoxide is the oxygenant of 0.001～0.05mol/L,
By being used for of constituting of more than one sodium hydroxide, yellow soda ash, sodium-acetate, ammoniacal liquor, volatile salt the free acidity of solution transferred to 0.0 ± 1.5 neutralizing agent.
The concentration of described primary phosphate is 0.003mol/L; 0.05mol/L; 0.09mol/L.
Described non-crystalline state phosphorization filming catalyst concentration is 0.002mol/L; 0.025mol/L; 0.04mol/L.
The concentration of described oxygenant is 0.002mol/L; 0.025mol/L; 0.04mol/L.
Described neutralizing agent free acidity is-1.4; 0; 1.4.
The present invention compares the beneficial effect that is produced with background technology:
1, because the present invention has adopted phosphoric acid salt, non-crystalline state phosphorization filming catalyzer, oxygenant, neutralizing agent to form phosphatization liquid as component in proportion, so it can obtain the lower phosphatize phosphate coat of porosity (being lower than crystalline state phosphatize phosphate coat and the common non-crystalline state phosphatize phosphate coat that contains molybdenum, tungsten compound) effectively, to steel and zinc (comprising pot galvanize) goods ADHESION OF PAINTS power better (being better than the common non-crystalline state phosphatize phosphate coat that contains molybdenum, tungsten compound).
2, because the present invention uses that price is not higher, the molybdenum of scarcity of resources or tungsten compound, thus cost lower (be about crystalline state phosphatize phosphate coat cost 55%, the common non-crystalline state phosphatize phosphate coat cost that contains molybdenum, tungsten compound 42%).
3, owing to do not need table to transfer before the phosphatization of the present invention, do not need the passivation sealing of hole after the phosphatization, so produce easy.
Embodiment:
Embodiment 1: get generation zinc phosphate 0.05mol/L, primary iron phosphate 0.001mol/L; Oxalic acid 0.01mol/L, citric acid 0.01mol/L, hydroxyethyl di 2 ethylhexyl phosphonic acid 0.003mol/L, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.003mol/L; Potcrate 0.03mol/L is as solute, the surplus water intaking is as solvent, mixing and stirring, as neutralizing agent its free acidity is transferred to 1.0 points (1 point=0.01N) with sodium hydroxide, under room temperature (20 ° ± 10 ℃), steel work or the zinc products of surface through degreasing, washing and rust cleaning immersed in the above phosphatization liquid, through 3～8min, or, can form the non-crystalline state phosphatize phosphate coat at product surface with above solution spraying 2～5min.
Embodiment 2: get generation zinc phosphate 0.04mol/L, primary iron phosphate 0.002mol/L; Primary calcium phosphate 0.003mol/L, citric acid 0.02mol/L, ethylenediamine tetraacetic phosphonic acids 0.005mol/L; Potcrate 0.025mol/L, SODIUMNITRATE 0.01mol/L is as solute, the surplus water intaking is as solvent, mixing and stirring, (1 point=0.01N) is under room temperature (20 ° ± 10 ℃) as neutralizing agent its free acidity to be transferred to 0.0 point with yellow soda ash, steel work or the zinc products of surface through degreasing, washing and rust cleaning immersed in the above phosphatization liquid, through 3～8min, or, can form the non-crystalline state phosphatize phosphate coat at product surface with above solution spraying 2～5min.
Embodiment 3: get generation zinc phosphate 0.03mol/L, primary iron phosphate 0.001mol/L, generation nickelous phosphate 0.001mol/L; Oxalic acid 0.01mol/L, citric acid 0.01mol/L, bios six phosphoric acid 0.003mol/L, EDTA (ethylenediamine tetraacetic acid (EDTA)) 0.003mol/L; SODIUMNITRATE 0.01mol/L, Sodium Nitrite 0.005mol/L are as solute, the surplus water intaking is as solvent, mixing and stirring, as neutralizing agent its free acidity is transferred to-0.5 point (1 point=0.01N) with yellow soda ash, under room temperature (20 ° ± 10 ℃), steel work or the zinc products of surface through degreasing, washing and rust cleaning immersed in the above phosphatization liquid, through 3～8min, or, can form the non-crystalline state phosphatize phosphate coat at product surface with above solution spraying 2～5min.
Embodiment 4: get generation zinc phosphate 0.002mol/L, generation manganous phosphate 0.04mol/L, tartrate 0.01mol/L; Propanedioic acid 0.005mol/L, hydroxyethyl di 2 ethylhexyl phosphonic acid 0.005mol/L; SODIUMNITRATE 0.02mol/L, Potcrate 0.02mol/L are as solute, the surplus water intaking is as solvent, mixing and stirring, as neutralizing agent its free acidity is transferred to 0.5 point (1 point=0.01N) with volatile salt, under room temperature (20 ° ± 10 ℃), steel work or the zinc products of surface through degreasing, washing and rust cleaning immersed in the above phosphatization liquid, through 3～8min, or, can form the non-crystalline state phosphatize phosphate coat at product surface with above solution spraying 2～5min.
Claims (10)
1, a kind of iron and zinc surface obtain the phosphatization liquid of non-crystalline state rete, it is characterized in that it comprises following component:
By more than one Zn
2+, Fe
2+, Mn
2+, Ca
2+, Mg
2+, Ni
2+, Al
2+The concentration that metal ion constitutes is the primary phosphate of 0.002～0.1mol/L,
The concentration that is made of hydroxyethyl di 2 ethylhexyl phosphonic acid, ethylenediamine tetraacetic phosphonic acids, the organic acid of EDTA in more than one the oxalic acid, propanedioic acid, maleic acid, citric acid, tartrate, bios six phosphoric acid, phosphonate derivative is the non-crystalline state phosphorization filming catalyzer of 0.001～0.05mol/L, this organic acid and above-mentioned metal ion have complexing or sequestering power
The concentration that is made of more than one oxymuriate, nitrate, nitrite, superoxide is the oxygenant of 0.001～0.05mol/L,
By being used for of constituting of more than one sodium hydroxide, yellow soda ash, sodium-acetate, ammoniacal liquor, volatile salt the free acidity of solution transferred to 0 ± 1.5 neutralizing agent.
2, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described primary phosphate is 0.003mol/L.
3, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described primary phosphate is 0.05mol/L.
4, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described primary phosphate is 0.09mol/L.
5, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, it is characterized in that described non-crystalline state phosphorization filming catalyst concentration is 0.002mol/L.
6, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, it is characterized in that described non-crystalline state phosphorization filming catalyst concentration is 0.025mol/L.
7, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, it is characterized in that described non-crystalline state phosphorization filming catalyst concentration is 0.04mol/L.
8, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described oxygenant is 0.002mol/L.
9, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described oxygenant is 0.025mol/L.
10, iron according to claim 1 and zinc surface obtain the phosphatization liquid of non-crystalline state rete, and the concentration that it is characterized in that described oxygenant is 0.04mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101152661A CN100494493C (en) | 2005-11-15 | 2005-11-15 | Phosphorization liquid for forming amorphous film coating on iron and zinc surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101152661A CN100494493C (en) | 2005-11-15 | 2005-11-15 | Phosphorization liquid for forming amorphous film coating on iron and zinc surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1966768A CN1966768A (en) | 2007-05-23 |
| CN100494493C true CN100494493C (en) | 2009-06-03 |
Family
ID=38075740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101152661A Expired - Fee Related CN100494493C (en) | 2005-11-15 | 2005-11-15 | Phosphorization liquid for forming amorphous film coating on iron and zinc surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100494493C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671824B (en) * | 2009-09-30 | 2011-02-02 | 重庆理工大学 | Magnesium alloy surface zinc-calcium series phosphating solution and conversion treatment process thereof |
| CN104651825B (en) * | 2015-03-13 | 2017-12-26 | 中国计量大学 | Petroleum machinery piece surface processing method |
| CN111167689B (en) * | 2020-01-03 | 2020-10-27 | 山东尚核电力科技有限公司 | Application method of steel pipe inside and outside plastic dipping production system |
-
2005
- 2005-11-15 CN CNB2005101152661A patent/CN100494493C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 酸度及NaNO3对钢铁常温磷化的影响. 王成，于宝兴，江峰等.腐蚀科学与防护技术，第13卷第3期. 2001 |
| 酸度及NaNO3对钢铁常温磷化的影响. 王成，于宝兴，江峰等.腐蚀科学与防护技术，第13卷第3期. 2001 * |
| 非晶型磷化成膜技术的研究. 李景尧，肖闯，石小刚.材料保护，第27卷第3期. 1994 |
| 非晶型磷化成膜技术的研究. 李景尧，肖闯，石小刚.材料保护，第27卷第3期. 1994 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1966768A (en) | 2007-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102002698B (en) | Anti-rust treating agent for nickel-plated battery steel shell and using method thereof | |
| JP3774415B2 (en) | A treatment solution for forming a black hexavalent chromium-free conversion coating on zinc and zinc alloy plating and a method of forming a black hexavalent chromium-free conversion coating on zinc and zinc alloy plating. | |
| US9228088B2 (en) | Composition for the alkaline passivation of zinc surfaces | |
| JP2806531B2 (en) | Zinc phosphate aqueous solution for surface treatment of iron or iron alloy material and treatment method | |
| US8337641B2 (en) | Treatment solution for forming black hexavalent chromium-free chemical conversion coating film on zinc or zinc alloy | |
| US9057133B2 (en) | Processing solution for forming hexavalent chromium free, black conversion film on zinc or zinc alloy plating layers, and method for forming hexavalent chromium free, black conversion film on zinc or zinc alloy plating layers | |
| US10876211B2 (en) | Compositions for application to a metal substrate | |
| AU2006246764A1 (en) | Method for preparing metallic workpieces for cold forming | |
| CN100334255C (en) | Method for applying a phosphate covering and use of metal parts thus phospated | |
| CN101278075B (en) | Phosphatising solution with hydrogen peroxide and chelating carboxylic acids | |
| JP2006342398A (en) | Green trivalent-chromium chemical conversion coating | |
| AU2004241000B2 (en) | Method and solution for coating metal surfaces with a phosphating solution containing water peroxide, produced metal object and use of said object | |
| CN100494493C (en) | Phosphorization liquid for forming amorphous film coating on iron and zinc surface | |
| AU708141B2 (en) | Zinc phosphatizing using low concentrations of copper and manganese | |
| US2326309A (en) | Method of producing phosphate coatings on ferrous metal articles | |
| AU705531B2 (en) | Zinc-phosphatizing using low concentrations of nickel and/or cobalt | |
| JPS5943883A (en) | Solution for chemically converting metal substrate and conversion therewith | |
| US20200199758A1 (en) | Improved method for nickel-free phosphating metal surfaces | |
| TW500828B (en) | Process for phosphating, after-washing and cathodic electro-dipcoating | |
| CN100392149C (en) | Phosphorizing solution containing soluble starch, and its preparing method | |
| CN104711561A (en) | Normal-temperature micro-slag rapid phosphatizing agent, and production method thereof | |
| CN1047706A (en) | The normal temperature antirust phosphating solution | |
| JPH0357192B2 (en) | ||
| CN107313041B (en) | A kind of HL series room temperature multifunction phosphide liquid | |
| TW201042082A (en) | Process for forming corrosion protection layers on metal surfaces |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090603 Termination date: 20121115 |